US9133054B2ActiveUtilityA1

White, opaque, β-spodumene/rutile glass-ceramic articles and methods for making the same

88
Assignee: CORNING INCPriority: Apr 13, 2012Filed: Oct 31, 2013Granted: Sep 15, 2015
Est. expiryApr 13, 2032(~5.8 yrs left)· nominal 20-yr term from priority
C03C 14/006Y10T428/315C03B 20/00C03C 21/002C03C 3/093C03C 10/0009C03C 14/00C03C 10/0027C03C 3/085C03B 32/02
88
PatentIndex Score
7
Cited by
56
References
18
Claims

Abstract

Crystallizable glasses, glass-ceramics, IXable glass-ceramics, and IX glass-ceramics are disclosed. The glass-ceramics exhibit β-spodumene ss as the predominant crystalline phase. These glasses and glass-ceramics, in mole %, include: 62-75 SiO 2 ; 10.5-17 Al 2 O 3 ; 5-13 Li 2 O; 0-4 ZnO; 0-8 MgO; 2-5 TiO 2 ; 0-4 B 2 O 3 ; 0-5 Na 2 O; 0-4 K 2 O; 0-2 ZrO 2 ; 0-7 P 2 O 5 ; 0-0.3 Fe 2 O 3 ; 0-2 MnOx; and 0.05-0.2 SnO 2 . Additionally, these glasses and glass-ceramics exhibit the following criteria: a. a ratio: [ Li 2 ⁢ O + Na 2 ⁢ O + K 2 ⁢ O + MgO + ZnO ] [ Al 2 ⁢ O 3 + B 2 ⁢ O 3 ]  between 0.7 to 1.5; b. a ⁢ ⁢ ratio ⁢ : ⁢ [ TiO 2 + SnO 2 ] [ SiO 2 + B 2 ⁢ O 3 ]  greater than 0.04. Furthermore, the glass-ceramics exhibit an opacity ≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness and colors an observer angle of 10° and a CIE illuminant F02 determined with specular reflectance included of a* between −3 and +3, b* between −6 and +6, and L* between 88 and 97.

Claims

exact text as granted — not AI-modified
We claim: 
     
       1. An IX, β-spodumene glass-ceramic comprising:
 a. a nominal composition, in mole percent (mole %), comprising:
 i. 62-75 SiO 2 ; 
 ii. 10.5-17 Al 2 O 3 ; 
 iii. 5-13 Li 2 O; 
 iv. 0-4 ZnO; 
 v. 0-8 MgO; 
 vi. 2-5 TiO 2 ; 
 vii. 0-4 B 2 O 3 ; 
 viii. 0-5 Na 2 O; 
 ix. 0-4 K 2 O; 
 x. 0-2 ZrO 2 ; 
 xi. 0-7 P 2 O 5    
 xii. 0-0.3 Fe 2 O 3 ; 
 xiii. 0-2 MnOx; and 
 xiv. 0.05-0.20 SnO 2 ; 
 
 b. a ratio: 
 
       
         
           
             
               
                 [ 
                 
                   
                     
                       Li 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   
                     
                       Na 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   
                     
                       K 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   MgO 
                   + 
                   ZnO 
                 
                 ] 
               
               
                 [ 
                 
                   
                     
                       Al 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                   + 
                   
                     
                       B 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                 
                 ] 
               
             
           
         
          between 0.7 to 1.5; 
         c. a ratio: 
       
       
         
           
             
               
                 [ 
                 
                   
                     TiO 
                     2 
                   
                   + 
                   
                     SnO 
                     2 
                   
                 
                 ] 
               
               
                 [ 
                 
                   
                     SiO 
                     2 
                   
                   + 
                   
                     
                       B 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                 
                 ] 
               
             
           
         
          greater than about 0.04; 
         d. one or more β-spodumene solid solutions comprising at least about 70 wt % of the crystalline phases of the glass-ceramic; 
         e. at least one Ti-containing crystalline phase comprising:
 i. about 2.5-8 wt % of the crystalline phases of the glass-ceramic, 
 ii. a morphology exhibiting a length ≧about 20 nm, and 
 iii. rutile; 
 
         f. an opacity comprising ≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness; 
         g. a depth of layer (DOL) ≧about 2% of an overall thickness of an article of the IX, β-spodumene glass-ceramic and a compressive stress (σ s ) in at least a portion of a surface of the article of at least about 300 MPa; and 
         h. optionally, one or more crystalline phase comprising:
 i. up to about 10 wt % of the crystalline phases of the glass-ceramic and 
 ii. a spinel structure, 
 
       
       wherein the at least one Ti-containing crystalline phase further comprises any one of anatase, a magnesium titanate, and an aluminum titanate; or further comprising mixtures of rutile and two or more of anatase, a magnesium titanate, and an aluminum titanate. 
     
     
       2. The IX, β-spodumene glass-ceramic according to  claim 1 , further comprising cordierite or mixtures of rutile, cordierite, and one or more of anatase, a magnesium titanate, and an aluminum titanate. 
     
     
       3. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the at least one Ti-containing crystalline phase comprises rutile comprising about 2-6 wt % of the crystalline phases of the glass-ceramic. 
     
     
       4. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the one or more β-spodumene solid solutions comprise at least about 75 wt % of the crystalline phases of the glass-ceramic. 
     
     
       5. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the optional one or more crystalline phase comprises:
 about 1-10 wt % of the crystalline phases of the glass-ceramic and 
 a Zn-containing spinel structure. 
 
     
     
       6. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the IX, β-spodumene glass-ceramic exhibits one or more of:
 a. a fracture toughness of greater than about 0.8 MPa·m 1/2 ; or 
 b. MOR of greater than 40,000 psi; or 
 c. a dielectric constant determined over a frequency between about 15 MHz-3.0 GHz at about 25° C. of less than about 10; or 
 d. a loss tangent determined over a frequency between about 15 MHz-3.0 GHz at about 25° C. of less of less than 0.02; or 
 e. a depth of layer (DOL) ≧about 40 μm in at least a portion of a surface of an article of the IX, β-spodumene glass-ceramic having a 2 mm overall thickness; or 
 f. a compressive stress (σ s ) of at least about 500 MPa in at least a portion of a surface of an article of the IX, β-spodumene glass-ceramic having a 2 mm overall thickness; or 
 g. any combination of two or more of the preceding. 
 
     
     
       7. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the glass-ceramic comprises a color presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02 determined from reflectance spectra measurements using a spectrophotometer with specular reflectance included comprising:
 a. CIE a* between −3 and +3; 
 b. CIE b* between −6 and +6; and 
 c. CIE L* between 88 and 97. 
 
     
     
       8. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the-β-spodumene solid solutions comprise a Li 2 O:Al 2 O 3 :SiO 2  ratio between about 1:1:4.5-1:1:8. 
     
     
       9. The IX, β-spodumene glass-ceramic according to  claim 1 , wherein the Ti-containing crystalline phase comprises an acicular morphology. 
     
     
       10. A glass-ceramic comprising:
 a. a composition, in mole %, comprising:
 i. 62-75 SiO 2 ; 
 ii. 10.5-17 Al 2 O 3 ; 
 iii. 5-13 Li 2 O; 
 iv. 0-4 ZnO; 
 v. 0-8 MgO; 
 vi. 2-5 TiO 2 ; 
 vii. 0-4 B 2 O 3 ; 
 viii. 0-5 Na 2 O; 
 ix. 0-4 K 2 O; 
 x. 0-2 ZrO 2 ; 
 xi. 0-7 P 2 O 5    
 xii. 0-0.3 Fe 2 O 3 ; 
 xiii. 0-2 MnOx; and 
 xiv. 0.05-0.20 SnO 2 ; 
 
 b. a ratio: 
 
       
         
           
             
               
                 [ 
                 
                   
                     
                       Li 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   
                     
                       Na 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   
                     
                       K 
                       2 
                     
                     ⁢ 
                     O 
                   
                   + 
                   MgO 
                   + 
                   ZnO 
                 
                 ] 
               
               
                 [ 
                 
                   
                     
                       Al 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                   + 
                   
                     
                       B 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                 
                 ] 
               
             
           
         
          between 0.7 to 1.5; 
         c. a ratio: 
       
       
         
           
             
               
                 [ 
                 
                   
                     TiO 
                     2 
                   
                   + 
                   
                     SnO 
                     2 
                   
                 
                 ] 
               
               
                 [ 
                 
                   
                     SiO 
                     2 
                   
                   + 
                   
                     
                       B 
                       2 
                     
                     ⁢ 
                     
                       O 
                       3 
                     
                   
                 
                 ] 
               
             
           
         
          greater than about 0.04; 
         d. one or more β-spodumene solid solutions comprising at least about 70 wt % of the crystalline phases of the glass-ceramic; 
         e. at least one Ti-containing crystalline phase comprising:
 i. about 2.5-8 wt % of the crystalline phases of the glass-ceramic, 
 ii. a morphology exhibiting a length≧about 20 nm, and 
 iii. rutile; 
 
         f. an opacity comprising≧about 85% over the wavelength range of 400-700 nm for an about 0.8 mm thickness; and 
         g. optionally, one or more crystalline phase comprising:
 i. up to about 10 wt % of the crystalline phases of the glass-ceramic; and 
 ii. a spinel structure. 
 
       
     
     
       11. The glass-ceramic according to  claim 10  wherein the at least one Ti-containing crystalline phase further comprises any one of anatase, a magnesium titanate, an aluminum titanate, or mixtures of rutile and two or more of anatase, a magnesium titanate, and an aluminum titanate. 
     
     
       12. The glass-ceramic according to  claim 10 , further comprising cordierite or mixtures of rutile, cordierite, and one or more of anatase, a magnesium titanate, and an aluminum titanate. 
     
     
       13. The glass-ceramic according to  claim 10 , wherein the at least one Ti-containing crystalline phase comprises rutile comprising about 2-6 wt % of the crystalline phases of the glass-ceramic. 
     
     
       14. The glass-ceramic according to  claim 10 , wherein the one or more β-spodumene solid solutions comprises at least about 75 wt % of the crystalline phases of the glass-ceramic. 
     
     
       15. The glass-ceramic according to  claim 10 , further comprising:
 a. the optional one or more crystalline phase comprising:
 i. about 1-10 wt % of the crystalline phases of the glass-ceramic and 
 ii. a Zn-containing spinel structure. 
 
 
     
     
       16. The glass-ceramic according to  claim 10 , wherein the glass-ceramic comprises at least a portion of at least one of an electronic devices or a portable computing device. 
     
     
       17. The glass-ceramic according to  claim 10 , wherein the glass-ceramic comprises a color presented in CIELAB color space coordinates for an observer angle of 10° and a CIE illuminant F02 determined from reflectance spectra measurements using a spectrophotometer with specular reflectance included comprising:
 i. CIE a* between −3 and +3; 
 j. CIE b* between −6 and +6; and 
 k. CIE L* between 88 and 97. 
 
     
     
       18. The glass-ceramic according to  claim 10 , wherein the Ti-containing crystalline phase comprises an acicular morphology.

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